Table ii



United States Patent 3,300,408 METHOD OF INHIBITING BACTERIA IN BRINE SYSTEMS Daniel S. Dustin, White Bear Lake, and Jack W. Sigan,

Minneapolis, Minn., assignors to Archer-Daniels-Midland Company, Minneapolis, Minn., a corporation of Delaware No Drawing. Filed Mar. 15, 1965, Ser. No. 440,020 5 Claims. (Cl. 210-64) This invention relates to the use of water soluble furfuryl aliphatic dialkyl quaternaries as inhibiting and killing bactericidal agents, or bacteriostats. More specifically this invention relates to the use of furfuryl aliphatic dimethyl quaternaries (where the aliphatic group is derived from fatty acids) in secondary oil recovery, as bactericides, to control sulfate-reducing bacteria and other micro-organisms.

This application is a continuation-in-part of our copending application Serial No. 108,767, filed May 9, 1961, now abandoned.

The literature provides no discovered information on furfuryl quaternaries as bactericides. The furfuryl dimethyl alkyl quaternary bromides have been prepared where the alkyl group is C through C These preparations were tested as stimulators for the parasympathetic nervous system (Weilmuenster and Jordan, I.A.C.S., 67, 415, 1945 and Nabenauer, US. Patent 2,185,220) where the alkyl group is C -C and the bromides are used as stimulators of neuromuscular mechanisms in the body. In general, there has been a relatively strong consenus that C to C alkyl chain quaternaries containing a benzyl group are most effective for inhibiting and killing bacteria growths and that longer alkyl chains are less effective and not particularly desirable.

Accordingly, it is an object of this invention to provide highly effective bacteria inhibiting and killing furfuryl based qua-ternary compounds having long chain aliphatic groups derived from fatty acids.

Another object of this invention is to provide the art with a method of using furfuryl aliphatic dialkyl ammonium quaternaries as inhibiting and killing bactericides when prepared from primary aliphatic amines having aliphatic hydrocarbon groups of 8 to 22 carbon atoms and preferably long chain aliphatic groups of about 16 to 18 carbon atoms derived from fatty acids and the character obtained from tall oil acids, rosin acids, coco acids, palmityl, oleic, lauryl, stearyl, or similar long chain aliphatic groups of this character.

A further and particular object of this invention is to provide a method of controlling sulfate-reducing bacteria with our preferred furfuryl aliphatic dimethyl quaternary in the recovery of secondary oil in the oil refining art and more particularly furfuryl hydrogenated-tallow dimethyl ammonium chloride.

To the accomplishment of the foregoing and related ends, this invention then comprises the features hereinafter set forth and more fully described and particularly pointed out by certain illustrative embodiments which are indicative of the ways in which the accomplishment of the herein described purposes are obtained.

In general the reactions involved in the preparation of the quaternaries, as herein described, are shown as follows:

wherein R is a saturated or unsaturated aliphatic group of 8 to 22 carbon atoms and preferably an aliphatic group of 16 to 18 carbon atoms derived from fatty acids. It will be recognized that other alkyl halides than the methyl chloride can be substituted. This would include materials such as ethyl'chloride, methyl bromide, and

the like. For example the furfuryl compounds contemplated herein have the following structure:

RH lwhere R is a C to C aliphatic hydrocarbon group R is furfuryl R" is a short chain alkyl X is a halogen atom Reaction I can be carried out in 10-15% benzene solution and the water of reaction is removed by azeotroping with the benzene. The theoretical amount of water is obtained. A preferred method is the vacuum removal of water.

Reaction II is carried out in a pressure vessel capable of withstanding 400 psi. pressure. The catalyst used is Raney Ni or Pd on charcoal, or a mixture of the two, or preferably copper chromite. The Raney Ni is used at 0.5% and the Pd at the 0.005% or 0.01% level as Pd and the copper chromite at 1-3%. The hydrogenation is carried out at 290-400 F. and 400 p.s.i. H pressure. The reaction usually takes 2-3 hours. After filtration to remove the catalyst, the product is ready for quarternization (Reaction III).

Reaction III is carried out in a pressure vessel capable of withstanding about 100 p.s.i. pressure. The secondary amine is dissolved in isopropanol and charged to the vessel. The vessel is purged with CH Cl and the temperature raised to 180200 F.; the pressure is then raised to psi. with CH Cl. Samples are withdrawn from the bomb and analyzed for free amine hydrohalide by titration. When the amine hydrohalide concentration starts to build up, 50 or 60% aqueous NaOH solution is forced into the vessel in order to neutralize the HCl formed. The reaction is considered finished when theamine hydrohalide and free amine total less than 1.5%.

The reaction is preferably run so that the concentration of the final product is 50% to 75% solids in the isopropanol.

To illustrate this invention, a preferred furfuryl hydrogenated-tallow dimethyl quaternary was prepared as follows:

amine nitrogen. Using secondary amine prepared by the preceding method the corresponding quaternary was prepared. 2175 gms. of amine, 700 gms. of NaHCO and Example I 900 gms. of isopropanol were charged to ancglugricglavlg. 5 The temperature was brought to and held at 2 T 2532 of hydrogenated-talk), g? while methyl chloride was intermittently introduced to ammes molecular were added 8 maintain a pressure of 60112 p.s.i.g. Intermittent ventfurfural over 3 70 mmute penod' The l was ing of CO was necessary after which the methyl chloride held at 41-5 and a Vacuum of i g was again fed into desired reaction pressures. After 7 cury was mamtamed to remove i of i en hours of reaction the batch was cooled, the autoclave no 3 Water appeared to be conllng 9 t e f was vented, and the reaction product filtered. consldered cornplete. Total reactlon time was 1 /z ours. The furfuryl coco dimethyl quaternary product com The schlfi.base so prepared was hydrogenated m a ig tained 76.5 quaternary salt, 1.6% free amine, 0.16% autoclave using 2% copper chromite as the catalyst. h amine hydmhalidey 002% ash and 506% Watch 2604100 and a hydmgen pressure of 400 t e 1 Illustrative of a method of application and use is as hydrogenation was considered complete after 6 hours. fOHOWS The total amine nitrogen content was 4.3% and the sec- Example III ondary content 2.90%. Theoretical total amine nitrogen a and theoretical secondary amine nitrogen content was calswondafy Q YCCOVEIY y Wafer i 1S Y Y culated to be 4.1%. affected by micro-organisms which either directly or in- The secondary amine was vacuum distilled to give a 20 directly accelerate and induces Sliming C Q I 94.8% distillation yield of a pale yellow liquid amine. Th slirning reduces filter efficiencies de c water The combining weight based on total amine nitrogen llllectwn Yates thfolfgh plugglflg of the Y lon. u a e-re uclng ac erla are 0 prlrne concern in analysls was 340. h l t d b t f The distilled amine was quaternized with methyl chlo- 25 t i d ft t t t th f f 1 I, ride to give a furfuryl hydrogenated-tallow dimethyl aml 0 es 5 wars o eva ua e e K mon.um chloride To 340 (ms of amine 108 ms ofiso phatlc.dlmethyl. ammon um. chlorides as bacterlostats 1 I 27 f t 105 3 against sulfate-reducing bacteria, ,Brines from five widely propano O g ii an th 1 2: a 3 separated areas were used in these tests The strains of a fautoc a e y c on e.gas at a ta 6 Desulfovibrio utilized in these studies were grown. from sufiiclent to P a pressme of 50 After, 5 30 untreated infectedsource. waters and the cultures were hours of reaction at a temperature of 190 F. the material then isolated and purified These fairly pure cultures showed free amme 017% amlfle hydrohahde were then reintroduced in various amounts (p.p.m.) into and the reaction was consldered substantially complete. Culture media made up ff the collected field Waters, cooling and Venting the P Was dlscharged and the media were then incubated under .controlled condifiltered. tions, and the time of growth in days, if any, was noted. Illustrative of another dilferent furfuryl aliphatic d1- Results areshown in Table I. i

TABLE I Specific Days noted for growth of Desuliovibrio Run Quatcmary used Aq. medium gravity of treated aq.mcdium p.p.m. p.p.m. p.p.m. p.p.m. p.p.m. 40p.p'.m. p.p.m.

1 Furfuryl hydro- Fresh water 1 1.015 None/21*" None/21." None/21 N0ne/21 None/21.4 None/211,- None/21.-

generaltelli-tallow r N nii l lfl 01 1 10131 3 p 7 2- do Brine 1.090 do d0 00..., "do".-. -.dO d0. Do. 3- Flr furyll cpco Freshwater 1.015 4days None/21 None/21... None/21. None/21". None/21 None/21. 11116 1y BJIHIIO- hl "d 4 h b i i ?l f Brine 1 1. 090 5days do 10 5 Furfurylhydro- Texas brine 1.020 12 days None/20 None/2on1 generated-tallow dimethy1ammo- Ilium chloride.

1 do 1.041 9days Illinois brine. l. 042 Arkansas brine 1. 050 Oklahoma bril1e 1. 065 11 days...

Illinois brine 1. 070 .do

*N one/21 means no growth of Disulfovibrio was noted after 21 days.

methyl quaternary, viz., furfuryl coco dimethyl quaternary, is the following:

Example II 1550 gms. of coco based primary amine, 690 gms. of furfuryl, and 150 gms. of benzine were charged to a 3-neck glass flask equipped with an agitator, thermometer, and water azeotrope separator. The reaction was carried out at 100120 C. with azeotropic removal of the water of reaction. 143 cc. of water were collected. The Schiff base so prepared was vacuum distilled at 0.2-0.3 mm. Hg to a residue temperature of 190 C. A distillation yield of 88% was obtained.

The distilled Schifi base was then hydrogenated in a Parr autoclave using 0.005% palladium catalyst. At 215- 304 F. and 400 p.s.i.g. hydrogen pressure the hydrogenation was substantially complete after 1 hours. The product analysis showed 5.03% total amine nitrogen, 4.66% secondary amine nitrogen, and 0.37% primary From the above it will be recognized that dependent upon the bacteria content the concentration (p.p.m.) of the quaternary will vary as the particular user finds necessary for his conditions. In many of the present tests an average of about 10-200 p.p.m. has been found to be satisfactory to reduce sliming and prevent filter clogging. However, more or less may be required and used according to water conditions, as known to those skilled in the art. In contrast to expectations the long chain hydrogenated-tallow furfuryl dimethyl ammonium chloride was surprisingly most eflectivein inhibiting or killing sulfate-reducing bacterial in oil well brines. In field application furfuryl hydrogenated-tallow dimethyl ammonium chloride quaternary was comparable to conventional and standard formulations of C -C chain alkyl compounds presently used in oil recovery.

In performance tests of phenol coefiicients (using the method described on page 87 of Ofiicial Methods of Analysis of the A. O.A.C., 8th ed., 1955), the hydrogen- 4.66% secondary amine nitrogen, and 0.37% primary ated-tal-low furfuryl quaternary was superior to the coco counterpart and lauryl benzyl dimethyl quaternary. The

6 A further series of innumerable personal tests involved mixing about one bottle cap full (about 1-2 oz.) of the fur'furyl quaternary of Example I to a glass of water and used as hair rinses. The results of softness and conditionfollowing is illustrative of test data of long chain aliphatic 5 i fo i g h h i proved amazing, D d ff furfurlfl q a r e (Where aliphatic g p is derived peared to be completely removed, not to reoccur on weekfrom iatty acids) in comparison to'several other recog- 1y Washing and like repeated rinsing of the hair mzed and commonly used materials" In testing relatively concentrated solutions of these TABLE I1 quaternaries, for toxicity, it is found that the hydrogen- 10 ated tallow, coco and cottonseed furfuryl dimethyl am- ,Phemlcoemcielltamoc monium chlorides were all quite similar toxicologically. Run Material .T- i The tests for acute oral toxicity (albino male rates), prigiij fggg ZZZ may skin and dermal irritation (rabbits) and eye irritation (rabbits) showed the following values: acute oral Fugmrylcomnsed dimethyl 1,000 260 LD-50 values are approximately 0.5 cc./kg. for the coco ggfi g sgfi dimethvl L000 320 f-urfuryl quaternary and 0.7 cc./kg. for the hydrogenated Fl-(llgialgilliniggd (methyl 960 so tallow and cottonseed furfuryl quaternaries. It would quaternary appear that the furfury-l long chain aliphatic quaternaries, gg g s dimethyl 20 where the aliphatic group is derived from fatty acids, Dicoco dime tliyl quatcrnary 52 29 may all be considered to be in the class of materials slightgz ig i gfi 900 140 ly toxic by accidental oral ingestion, moderate skin iri ig y 870 80 ritants and severe eye irritants, in a manner typical of Dodeeylbenzyltrimethyl 400 120 Cationic Surfactantsg g 24 60 20 Thus, while essentially finding application of the furfuryl long chain aliphatic quaternaries as useful in oil Additional tests showing the furfuryl long chain ali- W brinesi it i be recognized Qther advantages phatic ammonium chloride quaternaries (where the ali- Infuse as 'f q l i material phatic group is derived from fatty acids) are active against 30 P fonPPlaimns Supervlsed formulatlons for Escherichia coli and Staphylococcus aureus are shown in mg or klnmg athletlc foot and fungus growths annsepnc Table 111 The test method used was that described in cleaning solutions, and other analogous formulations are J.A.O.A.C., 41, No. 1, pages 34-36, 1958, using 200 possiblep p m of the quaternary, test water with a hardness of Modifications and alterations Of this invention Will 136 500 p,p,rn and numbers ntrol of 93-125 million apparent to those skilled in the art without departing from TABLE III (Gram negative) (Gram positive) Escherichia colz' Staphylocous aureus Run Quaternary used Exposure time, sec.

Survivor Percent Survivor Percent count kill count kill 1 Diiiydrogenated-tallow dimethyl ammonium chloride 2 Furtuwl hydrogenated-tallow dimethyl ammonium chloride. 3 Furfuryl hydrogenated-tallow 'dimethyl ammonium ehloi e. Furiuryl tallow dimethyl ammonium chloride Furiuryl cottonseed dimethyl ammonium chloride Furiuryl cottonseed dimethyl ammonium chloride Furfuryl coco dimethyl ammonium chloride Fui'fllryl coco dimethyl ammonium chloride Furturyl palmityl dimethyl ammonium chloride *TNTC means the number of surviving bacteria were too numerous to count.

Further tests were run against coli and S. aureus. The following comparisons were made at 500 ppm. water hardness and 30 and second counts.

the scope and spirit of this invention, and this invention should not be limited to the specific embodiments described herein.

TABLE IV Escherichia coli Staphylococcus aureus Run Quaternary used 4 Survivor Percent kill Survivor Percent kill count count 1 Furfuryi hydrogenated-tallow di- 'INTC TNTC *380/30 99. 999/99.999

methyl ammonium chloride. 2 Furfuryl coco dimethyl ammo- 39, 000/7, 800 99. 959/99. 992 14, 000/510 99. 892/99. 999

ninm chloride. 3 Furturyl palmityl dimethyi am- TNTC/120,000 199. 874 12, 000/270 99. 987/99. 999

monium chloride.

*30 see/60 sec. counts.

7 We claim: 1 1. A method for treating brine containing'bacteria, which comprises adding to said brine a compound of the formula:

compound is furfuryl tall ow dimethyl ammonium chloridef g 3; The method according to claim 1 wherein said compound is furfury-l hydrogenated-tallow dimethyl ammonium chloride.

4. A method forreducing s-liming and preventing filter clogging in aqueous brine systems for secondary oil'recovery, which comprises treating such brine with 10200 parts per million of acompound having the general formula:

l f v l "l where R is an aliphatic hydrocarbon having 8 -22 carbon atoms derived from fatty acids, R'is furfuryl, R" is selected from the group consisting of methyl and ethyl, and X is a halogen. 4

5. The method according to claim 4 wherein said compound is furfuryl hyd rogenated-ta-llow dimethyl ammonium chloride. 1

References Cited by, the Examiner UNITED STATES PATENTS 2,295,504 9/1942 Shelton 167-33 2,692,231 10/1954 Stayner et al. 252-855 2,733,206 1/1956 Prusick et "al. 252-855 OTHER REFERENCES La Susa, World Oil, April 1955, Production Section, pages 242-245. v

SAM ROSEN, Primary Examiner.- 

1. A METHOD FOR TREATING BRINE CONTAINING BACTERIA, WHICH COMPRISES ADDING TO SAID A COMPOUND OF THE FORMULA: 